Fluorine nitrate

Fluorine nitrate
Structural formulas of fluorine nitrate, showing its resonance structure
Ball-and-stick model of the fluorine nitrate molecule
Names
Other names
Nitryl hypofluorite
Identifiers
CAS Number
  • 7789-26-6 checkY
3D model (JSmol)
  • Interactive image
ChemSpider
  • 109875
PubChem CID
  • 123262
UNII
  • 1Q6BYH7F2B
CompTox Dashboard (EPA)
  • DTXSID20228502 Edit this at Wikidata
InChI
  • InChI=1S/FNO3/c1-5-2(3)4
    Key: VHFBTKQOIBRGQP-UHFFFAOYSA-N
  • FO[N+](=O)[O-]
Properties
Chemical formula
FNO3
Molar mass 81.002 g·mol−1
Density 2.217 g/L[1]
Melting point −175 °C (−283.0 °F; 98.1 K)
Boiling point −46 °C (−51 °F; 227 K)
Thermochemistry
Std enthalpy of
formation fH298)
+10.46 kJ/mol
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
Explosive gas
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references
Chemical compound

Fluorine nitrate is an unstable derivative of nitric acid with the formula FNO
3
. It is shock-sensitive.[1] Due to its instability, it is often produced from chlorine nitrate as needed[citation needed]. Fluorine nitrate is an inert molecule thought to play a significant role in atmospheric chemistry.[2]

History

In 1935, professor George H. Cady was first to synthesize fluorine nitrate and has since maintained a long and controversial history. In 1937, American chemist and biochemist Linus Pauling and one of his first graduate students, Lawrence O. Brockway, utilized electron diffraction intensities to determine the structure of the oxygen and fluorine bond perpendicular to the NO2 plane to be a non-planar structure. This would later be confirmed in 1963 and 1966 utilizing infrared spectra. [3]

In a 1995 study performed by Universität Tubingen in Germany, found through electron diffraction that the nitrogen–oxygen bond is surprisingly long at about a length of 150.7 ppm. This length is likely the result of the presence of electronegative atoms compared to other similar structures such as nitric acid.[3]

Synthesis and properties

Whilst not fully understood, it is thought that FNO
3
forms as a result of termolecular recombination of FO and NO
2
radicals. Fluorine Nitrate is prepared through the agitation of fluorine in its gaseous form, which will bubble through nitric acid or solid KNO3. Due to the shock sensitive nature of the compound, it is necessary to handle it with extreme caution:[4][5]

F2 + HNO3 → FNO3 + HF
F2 + KNO3 → FNO3 + KF

It decomposes in water to form oxygen gas, oxygen difluoride, hydrofluoric acid, and nitric acid.[1]

In fluorine nitrate, the oxygen atom bridging nitrogen and fluorine is in a rare oxidation state of 0 due to its electronegativity being lower than that of fluorine but higher than that of nitrogen. The role of electronegativity also is significant in the structure of fluorine nitrate. Through electron diffraction analysis, FNO
3
was determined to have a planar structure with a particularly long nitrogen-oxygen bond length.[6]

Fluorine nitrate has been linked to higher ionization potential due to the centrality of fluorine. This higher ionization potential is indicative of electron ionization of deeper shell orbitals.[5]

Applications

Since the 1990s, fluorine nitrate has been studied as a critical factor of atmospheric chemistry. It was in this period that fluorine nitrate began to be labeled as a reservoir species in the atmosphere.[5]

The relationship between the ionization potential and the highest occupied molecular orbital (HOMO) in fluorine nitrate was determined to be large. In a 1996 study, researchers asserted that the ionization potential of the HOMO in a molecule is a reflection of the electron-donating capacities of a molecule and as the ionization potential of the HOMO is lowered, subsequently the electron donating capacities of the molecule increase and become stronger.[5]

Despite the molecule’s inert nature, it is asserted by the 1996 study that fluorine nitrate may be the best possible reservoir species in the process of ozone depletion.[5]

References

  1. ^ a b c Ruff, Otto; Kwasnik, Walter (1935). "The fluorination of nitric acid. The nitroxyfluoride, NO3F". Angewandte Chemie. 48: 238–240. doi:10.1002/ange.19350481604.
  2. ^ Jensen, James O. (2005-03-07). "Vibrational frequencies and structural determination of fluorine nitrate". Journal of Molecular Structure: THEOCHEM. 716 (1): 11–17. doi:10.1016/j.theochem.2004.10.041. ISSN 0166-1280.
  3. ^ a b Oberhammer, H. (2002-03-13). "The NO bond in covalent nitrates and nitrites". Journal of Molecular Structure. 605 (2): 177–185. doi:10.1016/S0022-2860(01)00766-9. ISSN 0022-2860.
  4. ^ Elliott, Scott (1983-01-01). "Ultraviolet absorption spectra of FNO3 and HOF". Atmospheric Environment (1967). 17 (4): 759–761. doi:10.1016/0004-6981(83)90424-9. ISSN 0004-6981.
  5. ^ a b c d e Dianxun, Wang; Peng, Jiang; Qiyuan, Zhang (1996-11-29). "HeI photoelectron spectrum (PES) of fluorine nitrate, FONO2". Chemical Physics Letters. 262 (6): 771–775. doi:10.1016/S0009-2614(96)01154-2. ISSN 0009-2614.
  6. ^ Casper, Bernd; Mack, Hans-Georg; Oberhammer, Heinz (1995-04-01). "Gas-phase structures of some hypofluorites: FOSF5, FOSO2F, FOClO3 and FONO2". Journal of Fluorine Chemistry. Papers presented at the American Chemical Society - George H. Cady Memorial Symposium. 71 (2): 215. doi:10.1016/0022-1139(94)06031-G. ISSN 0022-1139.
  • v
  • t
  • e
Salts and covalent derivatives of the nitrate ion
HNO3 He
LiNO3 Be(NO3)2 B(NO3)4 RONO2
+CO3
+C2O4
NO3-
NH4NO3
HOONO2 FNO3
+F
Ne
NaNO3 Mg(NO3)2 Al(NO3)3
Al(NO3)4
Si P +SO4 ClONO2
+Cl
Ar
KNO3 Ca(NO3)2 Sc(NO3)3 Ti(NO3)4 VO(NO3)3 Cr(NO3)3 Mn(NO3)2 Fe(NO3)2
Fe(NO3)3
Co(NO3)2
Co(NO3)3
Ni(NO3)2 CuNO3
Cu(NO3)2
Zn(NO3)2 Ga(NO3)3 Ge As +SeO3 BrNO3
+Br
Kr
RbNO3 Sr(NO3)2 Y(NO3)3 Zr(NO3)4 NbO(NO3)3 MoO2(NO3)2 Tc Ru Rh(NO3)3 Pd(NO3)2
Pd(NO3)4
AgNO3
Ag(NO3)2
Cd(NO3)2 In(NO3)3 Sn(NO3)4 Sb4O4(OH)2(NO3)2 Te INO3
+IO3
Xe(NO3)2
CsNO3 Ba(NO3)2 * Lu(NO3)3 Hf(NO3)4 TaO(NO3)3 WO2(NO3)2 ReO3NO3 Os Ir3O(NO3)10 Pt(NO3)2 Au(NO3)3 Hg2(NO3)2
Hg(NO3)2
TlNO3
Tl(NO3)3
Pb(NO3)2 Bi(NO3)3
BiO(NO3)
Po(NO3)4 At Rn
FrNO3 Ra(NO3)2 ** Lr Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
 
* La(NO3)3 Ce(NO3)3
Ce(NO3)4
Pr(NO3)3 Nd(NO3)3 Pm(NO3)3 Sm(NO3)3 Eu(NO3)3 Gd(NO3)3 Tb(NO3)3 Dy(NO3)3 Ho(NO3)3 Er(NO3)3 Tm(NO3)3 Yb(NO3)3
** Ac(NO3)3 Th(NO3)4 PaO(NO3)3 UO2(NO3)2 Np(NO3)4 Pu(NO3)4 Am(NO3)3 Cm(NO3)3 Bk(NO3)3 Cf(NO3)3 Es Fm Md No
  • v
  • t
  • e
HF He
LiF BeF2 BF
BF3
B2F4
CF4
CxFy
NF3
N2F4
OF
OF2
O2F2
O2F
F Ne
NaF MgF2 AlF
AlF3
SiF4 P2F4
PF3
PF5
S2F2
SF2
S2F4
SF4
S2F10
SF6
ClF
ClF3
ClF5
HArF
ArF2
KF CaF2 ScF3 TiF3
TiF4
VF2
VF3
VF4
VF5
CrF2
CrF3
CrF4
CrF5
CrF6
MnF2
MnF3
MnF4
FeF2
FeF3
CoF2
CoF3
NiF2
NiF3
CuF
CuF2
ZnF2 GaF3 GeF4 AsF3
AsF5
SeF4
SeF6
BrF
BrF3
BrF5
KrF2
KrF4
KrF6
RbF SrF2 YF3 ZrF4 NbF4
NbF5
MoF4
MoF5
MoF6
TcF6 RuF3
RuF4
RuF5
RuF6
RhF3
RhF5
RhF6
PdF2
Pd[PdF6]
PdF4
PdF6
AgF
AgF2
AgF3
Ag2F
CdF2 InF3 SnF2
SnF4
SbF3
SbF5
TeF4
TeF6
IF
IF3
IF5
IF7
XeF2
XeF4
XeF6
XeF8
CsF BaF2 * LuF3 HfF4 TaF5 WF4
WF6
ReF6
ReF7
OsF4
OsF5
OsF6
OsF
7

OsF8
IrF3
IrF5
IrF6
PtF2
Pt[PtF6]
PtF4
PtF5
PtF6
AuF
AuF3
Au2F10
AuF5·F2
HgF2
Hg2F2
HgF4
TlF
TlF3
PbF2
PbF4
BiF3
BiF5
PoF4
PoF6
At RnF2
RnF6
Fr RaF2 ** Lr Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
* LaF3 CeF3
CeF4
PrF3
PrF4
NdF3 PmF3 SmF2
SmF3
EuF2
EuF3
GdF3 TbF3
TbF4
DyF3 HoF3 ErF3 TmF2
TmF3
YbF2
YbF3
** AcF3 ThF4 PaF4
PaF5
UF3
UF4
UF5
UF6
NpF3
NpF4
NpF5
NpF6
PuF3
PuF4
PuF5
PuF6
AmF3
AmF4
AmF6
CmF3 Bk Cf Es Fm Md No
PF6, AsF6, SbF6 compounds
  • AgPF6
  • KAsF6
  • LiAsF6
  • NaAsF6
  • HPF6
  • HSbF6
  • NH4PF6
  • KPF6
  • KSbF6
  • LiPF6
  • NaPF6
  • NaSbF6
  • TlPF6
AlF6 compounds
  • Cs2AlF5
  • Li3AlF6
  • K3AlF6
  • Na3AlF6
chlorides, bromides, iodides
and pseudohalogenides
SiF62-, GeF62- compounds
  • BaSiF6
  • BaGeF6
  • (NH4)2SiF6
  • Na2[SiF6]
  • K2[SiF6]
Oxyfluorides
  • BrOF3
  • BrO2F
  • BrO3F
  • LaOF
  • ThOF2
  • VOF
    3
  • TcO
    3
    F
  • WOF
    4
  • YOF
  • ClOF3
  • ClO2F3
Organofluorides
  • CBrF3
  • CBr2F2
  • CBr3F
  • CClF3
  • CCl2F2
  • CCl3F
  • CF2O
  • CF3I
  • CHF3
  • CH2F2
  • CH3F
  • C2Cl3F3
  • C2H3F
  • C6H5F
  • C7H5F3
  • C15F33N
  • C3H5F
  • C6H11F
with transition metal,
lanthanide, actinide, ammonium
  • VOF3
  • CrOF4
  • CrF2O2
  • NH4F
  • (NH4)2ZrF6
  • CsXeF7
  • Li2TiF6
  • Li2ZrF6
  • K2TiF6
  • Rb2TiF6
  • Na2TiF6
  • Na2ZrF6
  • K2NbF7
  • K2TaF7
  • K2ZrF6
  • UO2F2
nitric acids
bifluorides
  • KHF2
  • NaHF2
  • NH4HF2
thionyl, phosphoryl,
and iodosyl
  • F2OS
  • F3OP
  • PSF3
  • IOF3
  • IO3F
  • IOF5
  • IO2F
  • IO2F3